An organic polymer carrier, Z-N catalyst and preparation method and application thereof

Abstract

The application provides an organic polymer carrier, a Z-N catalyst and a preparation method and application thereof. The organic polymer carrier is obtained by copolymerization of monomers including divinylbenzene and unsaturated catechol ester monomers; wherein the unsaturated catechol ester monomer has a structure shown in formula I: the catalyst has good stereodirecting ability, and when used for propylene homopolymerization, the obtained polypropylene has high stereoregularity and relatively wide molecular weight distribution characteristics.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalysts, and particularly relates to an organic polymer carrier, a Z-N catalyst and a preparation method and application thereof, and particularly relates to a catalyst system of polypropylene with high stereoregularity and wide molecular weight distribution. BACKGROUND

[0002] Since the discovery of Z-N catalyst in the 1950s, with the innovation of polyolefin production technology and catalyst, the production and demand of polyolefin have been continuously increasing. In 2020, the global consumption of polyolefin was more than 200 million tons per year, and polypropylene was one of the fastest growing synthetic resins. It is predicted that the production and consumption of polypropylene will continue to grow in the next five years, and the global demand will exceed 800 million tons per year.

[0003] At present, the main industrialized polypropylene catalysts are Z-N type catalysts and metallocene catalysts, which are mainly used to produce high isotactic polypropylene. In addition, a small amount of syndiotactic polypropylene, atactic polypropylene and propylene-based elastomers are produced by using metallocene catalysts, post-metallocene catalysts and other catalysts. For the industrialized polypropylene production device, such as slurry polymerization, bulk polymerization or gas phase polymerization process, the catalyst needs to be loaded to control the morphology of the generated polymer and avoid the problems of reactor clogging or blockage.

[0004] The existing industrial catalysts mainly use inorganic carriers to support Z-N catalysts and metallocene catalysts. The inorganic carriers mainly include silicon dioxide, magnesium chloride, ethoxymagnesium, molecular sieve, etc. for supporting the catalysts. For Z-N catalysts, the commonly used carriers are ethoxymagnesium and anhydrous magnesium chloride, which are reacted with TiCl4 to form MgCl2-supported Z-N catalysts. During the preparation of the catalysts, electron donors or Lewis bases are usually added to regulate the micro-chemical environment of the metal active centers of the catalysts, thereby regulating the performance of the catalysts. For example, MgCl2-supported polypropylene catalysts usually include the following components: MgCl2 / TiCl4 / internal electron donor (ID) / silane external electron donor (ED). The common internal electron donors include phthalate internal electron donors (such as diisobutyl phthalate (DIBP) and di-n-butyl phthalate (DNBP)), phenolic ester internal electron donors, succinate internal electron donors, diether internal electron donors, etc. The internal electron donors or Lewis bases added in the catalyst system provide a unique electronic and steric environment for the surface of MgCl2 / TiCl4, thereby having a significant impact on the activity, stereoregularity, hydrogen regulation sensitivity, molecular weight and distribution of the products, etc. of the catalyst, and in addition, the surface crystal grain size of MgCl2, the content and distribution of Ti active centers can also be regulated. In the past three decades, most of the research in the development of high-performance polypropylene catalysts has focused on the design and selection of new internal electron donors. The Journal of Polymer Research “Progress in MgCl2 supported Ziegler-Natta catalyzed polyolefin products and applications” (Vol. 28, 2021, 45) reviews the internal electron donors used in polyolefin catalysts, including succinate (US20140200316), 1,3-diesters, diethers (US7022640), bicycloalkane diesters, bicycloalkene diesters (US20140005345), silicon-containing compounds (US8088872B2), etc. The above internal electron donors exhibit good polymerization activity and high chain regularity when used in propylene polymerization.

[0005] In the materials for food and drug packaging, polypropylene usually needs to have high isotacticity or low organic solvent extraction content to meet the requirements of the materials in these fields. The polypropylene catalyst supported by inorganic carriers usually has high polymerization activity and good control of polymer morphology, and high bulk density, but the inorganic carriers usually introduce additional impurities (in addition to Mg, Ti active centers), which limits their application in the development of high-purity polypropylene products. The organic polymer carrier is different from the reported inorganic carrier, and the POP carrier itself will not introduce impurities, thereby affecting the properties of the polymer. In addition, the organic carrier has controllable pore structure, high specific surface area, stable thermal performance, and is easy to functionalize; by designing and functionalizing the carrier, a high-performance or special polyolefin catalyst can be prepared. There are reports on porous organic carrier supported Z-N catalyst, which usually uses organic carriers containing carboxylic acid groups, hydroxyl groups, cyano groups, amino groups and other functional groups to prepare Z-N catalyst. However, the organic carrier type olefin catalyst is mainly polyethylene catalyst, and there are few reports on propylene polymerization. For example, "Sulfonated porous organic polymer supported Z-N polypropylene catalysts with high stereoregularity and broad molecular weight distribution" (343, 2022, 112151) in Microporous and Mesoporous Materials reports a POP carrier supported Z-N catalyst prepared by using p-styrene sulfonic acid functional monomer. When the catalyst is added with additional diphenyl ester as internal electron donor, the catalyst has a wide molecular weight distribution and a high isotacticity of more than 98%, but the isotacticity and activity of the polypropylene obtained by the catalyst system without adding additional internal electron donor are low, which has not reached the commercial level. SUMMARY

[0006] In order to solve the above problems, the purpose of the present application is to provide an organic polymer carrier, a Z-N catalyst and a preparation method and application thereof, which has good stereodirecting ability, and when used for propylene homopolymerization, the obtained polypropylene has high stereoregularity and wide molecular weight distribution characteristics.

[0007] In order to achieve the above purpose, the present application provides an organic polymer carrier, which is obtained by copolymerization of monomers including divinylbenzene and unsaturated hydroquinone ester monomers; wherein the unsaturated hydroquinone ester monomer has the structure shown in formula I:

[0008]

[0009] In formula I, R1, R2, R3, R6 are each independently selected from the group consisting of hydrogen, chlorine, fluorine, bromine, hydroxyl, C1-C6 straight chain alkyl and its derivatives, C1-C6 branched chain alkyl and its derivatives, cycloalkyl and its derivatives, aryl and its derivatives; x is 0-3, when x is 0, the carbon atom connected with R3 is directly connected with the benzene ring; R4, R5 are each independently selected from the group consisting of hydrogen, C1-C8 straight chain alkyl and its derivatives, C1-C8 branched chain alkyl and its derivatives, cycloalkyl and its derivatives, aryl and its derivatives.

[0010] According to a specific embodiment of the present application, preferably, in formula I, R1, R2, R3, R6 are each independently selected from the group consisting of hydrogen, chlorine, methyl, isobutyl, chlorine, fluorine, bromine, hydroxyl; R4, R5 are each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl, n-heptyl, 2-methylhexyl, 2-ethylpentyl, phenyl, vinyl, isopropenyl; x is 0 or 1.

[0011] According to a particular embodiment of the application, preferably, the unsaturated catechol ester monomer is selected from the group consisting of 4-allyl catechol dicarboxylate, 4-allyl catechol diacetate, 4-allyl catechol dipropionate, 4-allyl catechol di-n-butyrate, 4-allyl catechol diisobutyrate, 4-allyl catechol di-n-valerate, 4-allyl catechol di-n-hexanoate, 4-allyl catechol di-n-octanoate, 4-allyl catechol diisooctanoate, 4-allyl catechol di(2-methylheptanoate), 4-allyl catechol di(2-ethylhexanoate), 4-allyl catechol dibenzoate, 4-vinyl catechol diacetate, 4-vinyl catechol dipropionate, 4-vinyl catechol di-n-butyrate, 4-vinyl catechol diisobutyrate, 4-vinyl catechol di-n-valerate, 4-vinyl catechol di-n-hexanoate, 4-vinyl catechol di-n-octanoate, 4-vinyl catechol diisooctanoate, 4-vinyl catechol di(2-methylheptanoate), 4-vinyl catechol di(2-ethylhexanoate), 4-vinyl catechol dibenzoate, 4-allyl-6-methyl catechol dicarboxylate, 4-allyl-6-methyl catechol diacetate, 4-allyl-6-methyl catechol dipropionate, 4-allyl-6-methyl catechol di-n-butyrate, 4-allyl-6-methyl catechol diisobutyrate, 4-allyl-6-methyl catechol di-n-valerate, 4-allyl-6-methyl catechol di-n-hexanoate, 4-allyl-6-methyl catechol di-n-octanoate, 4-allyl-6-methyl catechol diisooctanoate, 4-allyl-6-methyl catechol di(2-methylheptanoate), 4-allyl-6-methyl catechol di(2-ethylhexanoate), 4-allyl-6-methyl catechol dibenzoate, 4-allyl-6-isobutyl catechol dicarboxylate, 4-allyl-6-isobutyl catechol diacetate, 4-allyl-6-isobutyl catechol dipropionate, 4-allyl-6-isobutyl catechol di-n-butyrate, 4-allyl-6-isobutyl catechol diisobutyrate, 4-allyl-6-isobutyl catechol di-n-valerate, 4-allyl-6-isobutyl catechol di-n-hexanoate, 4-allyl-6-isobutyl catechol di-n-octanoate, 4-allyl-6-isobutyl catechol diisooctanoate, 4-allyl-6-isobutyl catechol di(2-methylheptanoate), 4-allyl-6-isobutyl catechol di(2-ethylhexanoate), 4-allyl-6-isobutyl catechol dibenzoate, 4-allyl-6-chloro catechol dicarboxylate, 4-allyl-6-chloro catechol diacetate, 4-allyl-6-chloro catechol dipropionate, 4-allyl-6-chloro catechol di-n-butyrate, 4-allyl-6-chloro catechol diisobutyrate,4-allyl-6-chlororesorcinyl di-n-pentanoate, 4-allyl-6-chlororesorcinyl di-n-hexanoate, 4-allyl-6-chlororesorcinyl di-n-octanoate, 4-allyl-6-chlororesorcinyl diisooctanoate, 4-allyl-6-chlororesorcinyl di-(2-methylheptanoate), 4-allyl-6-chlororesorcinyl di-(2-ethylhexanoate), 4-allyl-6-chlororesorcinyl dibenzoate, 4-allyl-6-fluororesorcinyl dicarboxylate, 4-allyl-6-fluororesorcinyl diacetate, 4-allyl-6-fluororesorcinyl dipropionate, 4-allyl-6-fluororesorcinyl di-n-butyrate, 4-allyl-6-fluororesorcinyl diisobutyrate, 4-allyl-6-fluororesorcinyl di-n-pentanoate, 4-allyl-6-fluororesorcinyl di-n-hexanoate, 4-allyl-6-fluororesorcinyl di-n-octanoate, 4-allyl-6-fluororesorcinyl diisooctanoate, 4-allyl-6-fluororesorcinyl di-(2-methylheptanoate), 4-allyl-6-fluororesorcinyl di-(2-ethylhexanoate), 4-allyl-6-fluororesorcinyl dibenzoate, 4-allyl-6-bromoresorcinyl dicarboxylate, 4-allyl-6-bromoresorcinyl diacetate, 4-allyl-6-bromoresorcinyl dipropionate, 4-allyl-6-bromoresorcinyl di-n-butyrate, 4-allyl-6-bromoresorcinyl diisobutyrate, 4-allyl-6-bromoresorcinyl di-n-pentanoate, 4-allyl-6-bromoresorcinyl di-n-hexanoate, 4-allyl-6-bromoresorcinyl di-n-octanoate, 4-allyl-6-bromoresorcinyl diisooctanoate, 4-allyl-6-bromoresorcinyl di-(2-methylheptanoate), 4-allyl-6-bromoresorcinyl di-(2-ethylhexanoate), 4-allyl-6-bromoresorcinyl dibenzoate, 4-(1-chloroallyl)resorcinyl dicarboxylate, 4-(1-chloroallyl)resorcinyl diacetate, 4-(1-chloroallyl)resorcinyl dipropionate, 4-(1-chloroallyl)resorcinyl di-n-butyrate, 4-(1-chloroallyl)resorcinyl diisobutyrate, 4-(1-chloroallyl)resorcinyl di-n-pentanoate, 4-(1-chloroallyl)resorcinyl di-n-hexanoate, 4-(1-chloroallyl)resorcinyl di-n-octanoate, 4-(1-chloroallyl)resorcinyl diisooctanoate, 4-(1-chloroallyl)resorcinyl di-(2-methylheptanoate), 4-(1-chloroallyl)resorcinyl di-(2-ethylhexanoate), 4-(1-chloroallyl)resorcinyl dibenzoate, 4-allyl-6-hydroxyresorcinyl dicarboxylate, 4-allyl-6-hydroxyresorcinyl diacetate, 4-allyl-6-hydroxyresorcinyl dipropionate, 4-allyl-6-hydroxyresorcinyl di-n-butyrate, 4-allyl-6-hydroxyresorcinyl diisobutyrate, 4-allyl-6-hydroxyresorcinyl di-n-pentanoate, 4-allyl-6-hydroxyresorcinyl di-n-hexanoate,4-allyl-6-hydroxy-o-dihydroxybenzene di-n-octanoate, 4-allyl-6-hydroxy-o- dihydroxybenzene di-isooctanoate, 4-allyl-6-hydroxy-o-dihydroxybenzene di-(2- methylheptanoate), 4-allyl-6-hydroxy-o-dihydroxybenzene di-(2-ethylhexanoate), 4- allyl-o-dihydroxybenzene dibenzoate, 4-allyl-o-dihydroxybenzene diacrylate, 4- allyl-o-dihydroxybenzene dimethacrylate, or a combination of two or more thereof.

[0012] According to a specific embodiment of the present application, preferably, the mass fraction of the unsaturated o-dihydroxybenzene ester monomer is 20-70% calculated based on 100% of the mass of the organic polymer carrier; the content of the functional monomer in the carrier is determined by the addition amount of divinylbenzene and the unsaturated o-dihydroxybenzene ester functional monomer.

[0013] The present application also provides a preparation method of the above-mentioned organic polymer carrier, which comprises the following steps: using monomers comprising the divinylbenzene, the unsaturated o-dihydroxybenzene ester monomer and additional monomers as raw materials, and copolymerizing to obtain the organic polymer carrier; the mass ratio of the additional monomer to divinylbenzene is 0-1:1; the mass ratio of the unsaturated o-dihydroxybenzene ester monomer to divinylbenzene is 0.2-2:1.

[0014] According to a specific embodiment of the present application, preferably, the organic polymer carrier is prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization.

[0015] According to a specific embodiment of the present application, preferably, the organic polymer carrier is prepared by the dispersion polymerization, which comprises the following steps: adding divinylbenzene, unsaturated o-dihydroxybenzene ester monomer, additional monomer in a dispersion solvent, then adding a stabilizer and an initiator, stirring and dispersing, and then reacting at 50-80°C for 5-12 hours to obtain the organic polymer carrier, denoted as POP-Ph-(OCO)2; more preferably, the obtained organic polymer carrier can be further washed with a dispersion solvent to remove impurities and dried; the obtained organic carrier has a narrow dispersion and good fluidity.

[0016] According to a specific embodiment of the present application, preferably, in the above preparation method, the additional monomer comprises one or a combination of two or more of styrene, alkyl-substituted styrene, chloromethyl-substituted styrene, methacrylic acid, methacrylate, hydroxyalkyl methacrylate, for example, hydroxyethyl methacrylate.

[0017] According to the specific embodiment of the present application, preferably, in the above preparation method, the dispersing solvent comprises C1-C4 alcohol, water, additional solvent, the additional solvent comprises tetrahydrofuran and / or fatty acid ester; the mass ratio of the C1-C4 alcohol to water is 5-15:1; the mass ratio of the additional solvent to C1-C4 alcohol is 0-2:1; during the preparation of the carrier, the solubility parameter of the solvent system is adjusted by the solvent, so as to control the pore structure and morphology of the prepared carrier.

[0018] According to the specific embodiment of the present application, preferably, in the above preparation method, the C1-C4 alcohol comprises one or more than two combinations of methanol, ethanol, propanol, isopropanol, 1-butanol and isobutanol.

[0019] According to the specific embodiment of the present application, preferably, in the above preparation method, the fatty acid ester comprises ethyl acetate and / or butyl acetate.

[0020] According to the specific embodiment of the present application, preferably, in the above preparation method, the mass ratio of the total amount of monomer addition to the dispersing solvent is 1:5-20, so as to make the system uniformly dispersed.

[0021] According to the specific embodiment of the present application, preferably, in the above preparation method, the stabilizer is polyvinyl alcohol and / or polypropylene oxide-polyethylene oxide copolymer.

[0022] According to the specific embodiment of the present application, preferably, in the above preparation method, the weight average molecular weight of the stabilizer is 1000-100000.

[0023] According to the specific embodiment of the present application, preferably, in the above preparation method, the mass ratio of the amount of the stabilizer to the total amount of monomer addition is 0.5-5:100.

[0024] According to the specific embodiment of the present application, preferably, in the above preparation method, the initiator is azobisisobutyronitrile (AIBN) and / or dibenzoyl peroxide (BPO).

[0025] According to the specific embodiment of the present application, preferably, in the above preparation method, the mass ratio of the amount of the initiator to the total amount of monomer addition is 0.5-3:100.

[0026] According to the specific embodiment of the present application, preferably, in the above preparation method, the divinylbenzene is pretreated divinylbenzene, and the pretreatment is removal of the polymerization inhibitor.

[0027] The present application also provides a Z-N catalyst, the raw material composition of which comprises 60-85 wt% of the organic polymer carrier, 1-5 wt% of magnesium compound calculated as magnesium element, 1-5 wt% of titanium compound calculated as titanium element and 0-5 wt% of internal electron donor, based on 100% of the mass of the Z-N catalyst.

[0028] According to a specific embodiment of the present application, preferably, the content of the organic polymer carrier is 65-80 wt%, the content of magnesium element is 2-4 wt% and the content of titanium element is 2-4 wt%.

[0029] According to a specific embodiment of the present application, preferably, the magnesium compound is RMgX or R'MgR"; each of R, R' and R" is independently selected from C1-C8 alkyl and derivatives thereof, aryl and derivatives thereof, alkoxy and derivatives thereof, and X is fluorine, chlorine, bromine or iodine.

[0030] According to a specific embodiment of the present application, preferably, each of R, R' and R" is independently selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl and substituted phenyl.

[0031] According to a specific embodiment of the present application, preferably, the magnesium compound is one or a combination of two or more of alkyl halogenated magnesium compound, alkyl magnesium compound and alkoxy halogenated magnesium compound, and more preferably is alkyl chlorinated magnesium compound.

[0032] According to a specific embodiment of the present application, preferably, the magnesium compound comprises one or a combination of two or more of methyl magnesium chloride, n-butyl magnesium chloride, isobutyl magnesium chloride, t-butyl magnesium chloride, benzyl magnesium chloride, ethyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, n-butyl magnesium bromide, benzyl magnesium bromide, methyl magnesium iodide, t-butyl magnesium iodide, benzyl magnesium iodide, n-butyl magnesium iodide, methyl magnesium fluoride, t-butyl magnesium fluoride, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, ethoxy magnesium chloride; and the magnesium compound is contacted with the organic polymer carrier to prepare a porous organic carrier treated with magnesium compound, denoted as POP-Ph-(OCO)2...MgX.

[0033] According to a specific embodiment of the present application, preferably, the titanium compound is titanium tetrachloride; and the porous organic carrier treated with magnesium compound (POP-Ph-(OCO)2...MgX) is further reacted with titanium tetrachloride to obtain the Z-N catalyst, denoted as POP-Ph-(OCO)2...MgX / TiCl4.

[0034] The Z-N catalyst of the present application can optionally add additional internal donor (ID) to obtain the Z-N catalyst, denoted as POP-Ph-(OCO)2...MgX / TiCl4 / ID; according to the specific embodiments of the present application, preferably, the internal donor is one or a combination of two or more of diester compound, diphenate compound, diol ester compound, succinate compound, diether compound.

[0035] According to the specific embodiments of the present application, preferably, the internal donor includes one or a combination of two or more of diisobutyl phthalate (DIBP), di-n-butyl phthalate (DNBP), 9,9-dimethoxyfluorene, 2,3-diisopropyl succinic acid diisobutyl ester, 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate (IAIPPDB), 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether (IAIPDMP).

[0036] The present application also provides a preparation method of the above-mentioned Z-N catalyst, which comprises the following steps:

[0037] Under anhydrous and anaerobic conditions, the organic polymer carrier is added into an inert solvent, the magnesium compound is added, and after reaction at 0-50°C for 15-120 minutes, the unreacted magnesium compound is filtered, and then the inert solvent and titanium tetrachloride are added, and after reaction at 0-120°C for 15-180 minutes, the internal donor (which can be optionally added) is added, and after reaction at 50-120°C for 15-180 minutes, the Z-N catalyst is obtained by washing with the inert solvent.

[0038] In the Z-N catalyst of the present application, the content of the functional monomer (the unsaturated diphenate functional monomer) in the organic polymer carrier is generally 0.5 mmol / g of carrier to 5 mmol / g of carrier, preferably 1 mmol / g of carrier to 4 mmol / g of carrier; the content of the functional monomer is usually regulated by the ratio of the amount of the functional monomer to the amount of divinylbenzene (DVB) monomer added during the preparation of the carrier; the ratio of the amount of the magnesium compound reagent (in terms of the number of moles of magnesium Mg) to the amount of the carrier is 1 mmol / g of carrier to 30 mmol / g of carrier, preferably 3 mmol / g of carrier to 20 mmol / g of carrier; generally, an excess of Ti metal compound, such as TiCl4, is added for catalyst loading, and the amount of the Ti metal compound added (in terms of the number of moles of titanium Ti) is generally 5 mmol / g of carrier to 200 mmol / g of carrier, preferably 50 mmol / g of carrier to 150 mmol / g of carrier; the ratio of the amount of the internal donor to the amount of the carrier is 0 to 0.3 g of internal donor / g of carrier.

[0039] The application also provides a Z-N catalyst system, which comprises the Z-N catalyst, an external electron donor and a cocatalyst.

[0040] According to a specific embodiment of the application, preferably, the external electron donor comprises a silane external electron donor.

[0041] According to a specific embodiment of the application, preferably, the silane external electron donor comprises one or a combination of two or more of cyclohexylmethyldimethoxysilane (C-donor), dicyclopentadiene dimethoxysilane (D-donor), diisopropyl dimethoxysilane (P-donor), diisobutyl dimethoxysilane (B-donor) and tetraethoxysilane (TEOS).

[0042] According to a specific embodiment of the application, preferably, the molar ratio of silicon in the silane external electron donor to titanium in the Z-N catalyst is 1-50.

[0043] According to a specific embodiment of the application, preferably, the cocatalyst comprises an alkyl aluminum compound, which is Al(R”’)3, and R”’ is a C1-C6 alkyl group; in addition, the added alkyl aluminum compound can also act as a decontaminant of the polymerization system.

[0044] According to a specific embodiment of the application, preferably, R”’ is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl.

[0045] According to a specific embodiment of the application, preferably, the cocatalyst is triethyl aluminum.

[0046] According to a specific embodiment of the application, preferably, the molar ratio of aluminum in the alkyl aluminum compound to titanium in the Z-N catalyst is 10-500.

[0047] The application also provides an application of the above Z-N catalyst or the above Z-N catalyst system in olefin polymerization.

[0048] According to a specific embodiment of the application, preferably, the olefin polymerization is propylene homopolymerization, copolymerization of propylene and ethylene or copolymerization of α-olefin.

[0049] According to a specific embodiment of the application, preferably, the α-olefin is butene and / or isobutene.

[0050] According to a specific embodiment of the application, preferably, the olefin polymerization is gas phase polymerization, bulk polymerization or slurry polymerization.

[0051] According to a specific embodiment of the application, preferably, the reaction temperature of the slurry polymerization is 30-80℃, and the reaction pressure is 0.1-2.0 Mpa.

[0052] According to the specific embodiment of the present application, preferably, the solvent of the slurry polymerization is C5-C 10 alkane, more preferably hexane.

[0053] According to the specific embodiment of the present application, preferably, the reaction pressure of the bulk polymerization is 2.8-4.0 MPa, and the reaction temperature is 68-72℃; hydrogen is usually used in the polymerization process to adjust the polymer molecular weight or polymer melt index.

[0054] The porous organic polymer carrier loaded Z-N type olefin catalyst of the present application, from the perspective of the carrier, a functional monomer containing unsaturated double bond catechol ester is polymerized with a monomer such as divinylbenzene to obtain a porous organic polymer (POP) carrier (denoted as POP-Ph-(OCO)2), the catechol ester functional group in the carrier interacts with the active center Mg and Ti, thereby preparing a porous organic polymer (POP) type Z-N catalyst (denoted as POP-Ph-(OCO)2 / RMgX / TiCl4), and an internal electron donor can be selected to be added; wherein the selected functional monomer not only has an important influence on the preparation of the carrier, directly affecting the specific surface area, pore volume, bulk density, fluidity, etc. of the prepared carrier, but also due to the introduction of catechol ester functional groups on the carrier, the chelate structure of the group can play the role of an internal electron donor in the Z-N catalyst, and the micro-chemical environment of the active center Ti and Mg is modified, and the prepared catalyst has good stereospecificity and catalyst activity, and the product catalyzed by the catalyst has a relatively wide molecular weight distribution; during the preparation of the catalyst, even if no additional internal electron donor is added (an additional internal electron donor can also be selected to be added), the obtained catalyst still has stereospecificity, and the isotacticity of polypropylene can reach more than 98%; in addition, the POP carrier type polypropylene catalyst prepared by using the functional monomer has the characteristic of wide molecular weight distribution, and the molecular weight distribution coefficient is between 8-20; when used for propylene polymerization, by adding a silane external electron donor and a triethylaluminum cocatalyst, the obtained polymer has a relatively high isotacticity, which can reach more than 98%, the TREF high-temperature elution peak temperature (high-isotactic polypropylene fraction) is higher than that of other commercial high-isotactic polypropylene catalysts, and the high-temperature elution peak can reach 124℃; in addition, the product has a relatively wide molecular weight distribution, and the molecular weight distribution coefficient is between 8-20.

[0055] The organic polymer supported Z-N olefin polymerization catalyst system of the present application needs to add additional external electron donors in polymerization, and both of them need to be matched to play the excellent performance of high catalytic activity and high orientation ability; generally, the cocatalyst AlEt3 can be complexed with the internal electron donor, causing the Ti atom to lose stability with the internal electron donor, and will reoccupy the random active position complexed by the internal electron donor, causing the decline of the orientation ability of the catalyst; the addition of the external electron donor can be combined with AlEt3 in priority, avoiding the loss of the internal electron donor, reducing the amount of the internal electron donor compound removed by AlEt3, and ensuring the stability of the stereospecific center; thus, additional external electron donors need to be supplemented in the polymerization process, so that the prepared polymer has higher isotacticity. DETAILED DESCRIPTION

[0056] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present application, the technical solutions of the present application will be described in detail below, but it cannot be understood as limiting the scope of the implementation of the present application.

[0057] In the present application, divinylbenzene (DVB) can use commercially available monomers with 55% or 80% DVB content, which all need to be pretreated before use, and the polymerization inhibitor is removed before use. There are many methods for removing the polymerization inhibitor in the prior art, such as washing with NaOH solution and distilled water for divinylbenzene and styrene, and using a neutral alumina column to remove the polymerization inhibitor for additional monomers such as hydroxyethyl methacrylate.

[0058] In the present application, the unsaturated double bond-containing catechol ester functional monomer can be prepared by esterification reaction of the catechol containing unsaturated double bond with the corresponding acid according to the prior art.

[0059] In the present application, the molecular weight and its distribution of the polymer prepared by olefin polymerization are obtained by gel permeation chromatography (GPC) of Polymer Char company; the isotacticity of the polymer is obtained by n-heptane extraction test (referring to standard GBT 2412-2008); the internal electron donor content can be determined by extraction and gas chromatography.

[0060] In the present application, the specific surface area of the prepared organic polymer carrier is tested by Nova 2000e using BET nitrogen adsorption method, and the specific surface area of the carrier prepared in the present application is controlled to be greater than 100 m 2 / g, between 100-600 m 2 / g, and the pore volume is greater than 0.2 ml / g.

[0061] Preparation of unsaturated catechol ester functional monomers

[0062] Preparation Example 1

[0063] The present preparation example provides a 4-allyl catechol diacetate monomer, which is prepared by the following steps:

[0064] The 4-allyl catechol diacetate compound can be prepared by esterification of 4-allyl catechol (CAS: 1126-61-0, 97%) with acetic anhydride at 20-50°C under normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain 4-allyl catechol diacetate (reference: Alejandro Madrid Villegas et al., New Catechol Derivatives of Safrole and Their Antiproliferative Activity towards Breast Cancer Cells, Molecules 2011, Vol. 16, No. 6, P4632-4641). Specifically, 6.0 g of 4-allyl catechol, 10 g of acetic anhydride, 300 ml of dried dichloromethane solvent, and 0.02 g of 4-dimethylaminopyridine (DMAP) are added to a 500 ml reaction kettle, and reacted at room temperature for 3 hours. Then, 10 g of anhydrous K2CO3 is added, and esterification is carried out under normal pressure to obtain a crude product. After filtration, neutralization, water washing, and distillation under reduced pressure, 4-allyl catechol diacetate is obtained with a yield of 92%.

[0065] Preparation Example 2

[0066] The present preparation example provides a 4-allyl catechol dibenzoate monomer, which is prepared by the following steps:

[0067] The 4-allyl catechol dibenzoate compound can be prepared by esterification of 4-allyl catechol (CAS: 1126-61-0, 97%, alias: 4-allyl-1,2-benzenediol) with benzoic acid at 20-50°C under normal pressure to obtain a crude product, and then distilling under reduced pressure to obtain 4-allyl catechol dibenzoate. Specifically, 6.0 g of 4-allyl catechol, 12 g of benzoic acid, 300 ml of dried CH2Cl2 solvent, and 0.02 g of DMAP are added to a 500 ml reaction kettle, and reacted at room temperature for 3 hours. Then, 10 g of anhydrous K2CO3 is added, and esterification is carried out under normal pressure to obtain a crude product. After filtration, neutralization, water washing, and distillation under reduced pressure, 4-allyl catechol dibenzoate is obtained with a yield of 91%.

[0068] Preparation Example 3

[0069] The present preparation example provides a 4-allyl-6-bromo catechol diisobutyrate monomer, which is prepared by the following steps of esterification of 4-allyl 6-bromo catechol with isobutyric acid:

[0070] (1) The preparation method of 4-allyl-6-bromocatechol can refer to the literature (Hypervalent iodine-mediated oxygenative phenol dearomatization reactions, Laurent Pouysegu et al., Tetrahedron journal, 2010, Vol. 66, No. 31, pp. 5908-5917), and the catechol compound is obtained by demethylation reaction of 6-bromo-4-allyl-2-methoxyphenol (CAS: 5746-37-2) with a yield of about 67%: 4.86 g of 6-bromo-4-allyl-2-methoxyphenol is added into a 500 ml glass reaction bottle, then 1.1 mol equivalent of 2-iodoxybenzoic acid (CAS: 61717-82-6) in tetrahydrofuran solution is added, and the reaction is carried out at room temperature (25°C, the same below) for 3 hours, then an excess of freshly prepared aqueous sodium dithionite (CAS: 7775-14-6) solution is added, and after reaction for 1 h, filtration and distillation under reduced pressure, 4-allyl 6-bromocatechol is obtained with a yield of 67%.

[0071] (2) 6.0 g of 4-allyl 6-bromocatechol, 12 g of isobutyric acid, 300 ml of dried CH2Cl2 solvent and 0.02 g of DMAP are added into a 500 ml reaction kettle, and the reaction is carried out at room temperature for 3 hours, then 10 g of anhydrous K2CO3 is added, and esterification is carried out under normal pressure to obtain a crude product, which is filtered, neutralized, washed with water and distilled under reduced pressure to obtain 4-allyl-6-bromocatechol diisobutyrate with a yield of 89%.

[0072] Preparation Example 4

[0073] The present preparation example provides a 4-allyl-6-bromocatechol diacetate monomer, which is prepared by the following steps:

[0074] 6.0 g of 4-allyl 6-bromocatechol, 12 g of acetic acid, 300 ml of dried CH2Cl2 solvent and 0.02 g of DMAP are added into a 500 ml reaction kettle, and the reaction is carried out at room temperature for 3 hours, then 10 g of anhydrous K2CO3 is added, and esterification is carried out under normal pressure to obtain a crude product, which is filtered, neutralized, washed with water and distilled under reduced pressure to obtain 4-allyl-6-bromocatechol diacetate with a yield of 91%.

[0075] Preparation Example 5

[0076] The present preparation example provides a 4-allyl-6-bromocatechol dibenzoate monomer, which is prepared by the following steps:

[0077] In a 500 ml reactor, 5.8 g of 4-allyl-6-bromoresorcinol and 11.8 g of benzoic acid were added to 300 ml of dry CH2Cl2solvent and 0.02 g of DMAP, and the reaction was carried out at room temperature for 3 hours. Then, 10 g of anhydrous K2CO3was added, and esterification was carried out at normal pressure to obtain a crude product. After filtration, neutralization, water washing, and reduced pressure distillation, 4-allyl-6-bromoresorcinol dibenzoate was obtained in a yield of 92%.

[0078] Example 1

[0079] This example provides a Z-N catalyst prepared by the following steps:

[0080] (1) Preparation of a porous organic polymer support:

[0081] In a 250 ml glass reactor, 100 ml of ethanol and 12 ml of deionized water and 20 ml of butyl acetate were added, followed by 5.0 g of divinylbenzene (Aldrin reagent, 55%) and 2.5 g of 4-allyl resorcinol diacetate. After stirring at room temperature for 5 min, 2% of PVA (polyvinyl alcohol, degree of polymerization 1750) based on the mass of the monomer was added, and the stabilizer was completely dissolved by stirring at 45°C for 1 h. Then, 2.0% of AIBN based on the mass of the monomer was added, and the temperature was raised to 70°C, and the reaction was carried out for 3 hours. Then, the temperature was raised to 80°C, and the reaction was carried out for 12 hours, with stirring at 350 rpm. After filtration, the product was washed with a mixture of ethanol and water (9:1 by volume) 1000 ml for 3 times, and then filtered and dried to obtain 4.9 g of a free-flowing porous organic polymer support POP-1. The specific surface area of the support was 285 m 2 / g, and the pore volume was 0.42 ml / g.

[0082] (2) Preparation of a Z-N catalyst:

[0083] In a 250 ml glass reactor, 2 g of the support POP-1 prepared using 4-allyl resorcinol diacetate as the functional monomer was added, and 100 ml of toluene was stirred, followed by the addition of 10 ml of a 3M methylmagnesium chloride Grignard reagent at room temperature. The stirring was continued for 2 hours, and then the product was filtered and washed with toluene twice. Then, 50 ml of toluene was added, and 50 ml of TiCl4was added dropwise at room temperature. The temperature was raised to 60°C, and the reaction was carried out for 2 hours. After filtration, the product was washed with toluene and hexane each for 3 times, and then dried to obtain a free-flowing catalyst particle, which was denoted as Cat-1. The Mg content of the catalyst Cat-1 was 2.8%, the Ti content was 4.1%, and the organic polymer support content was 81%.

[0084] Example 2

[0085] This example provides a Z-N catalyst prepared by the following steps:

[0086] (1) Preparation of porous organic polymer support:

[0087] In a 250 ml glass reactor, 100 ml of ethanol and 10 ml of deionized water and 15 ml of tetrahydrofuran were added, then 5.0 g of divinylbenzene (Aldrin reagent, 80%) and 3.0 g of 4-allyl catechol dibenzoate (98.5%) were added, stirred at room temperature for 5 min, then 2% of monomer mass of polyvinyl alcohol PVA (PVA, degree of polymerization 1750) was added, stirred at 45°C for 1 h, the stabilizer was completely dissolved, 2.0% of monomer mass of AIBN was added, the temperature was raised to 70°C, and the reaction was carried out for 3 hours, then the temperature was raised to 80°C, and the reaction was carried out for 12 hours, the stirring speed was 350 rpm, after filtration, 1000 ml of mixed solvent of ethanol and water (9:1 by volume) was added for washing 3 times, and after filtration and drying, 5.8 g of free-flowing porous organic polymer support POP-2 was obtained. The specific surface area of the support was 485 m 2 / g, and the pore volume was 0.47 ml / g;

[0088] (2) Preparation of Z-N catalyst:

[0089] In a 250 ml glass reactor, 2 g of the support POP-2 prepared using 4-allyl catechol dibenzoate functional monomer was added, 100 ml of toluene was added and stirred, then 8 ml of 3M methyl magnesium chloride Grignard reagent was added at 5°C, stirred for 2 hours, after filtration, washed with toluene twice, then 50 ml of toluene was added, 35 ml of TiCl4 was added dropwise at room temperature, reacted for 1 hour, then the temperature was raised to 80°C, reacted for 1 hour, then filtered, added 50 ml of toluene and 30 ml of TiCl4, reacted at 80°C for 2 hours, after the reaction was completed, filtered, washed with toluene and hexane each for 3 times, and dried to obtain free-flowing catalyst particles, which were recorded as Cat-2. The Mg content of the catalyst Cat-2 was 2.5%, the titanium content was 2.7%, and the organic polymer support content was 82%.

[0090] Example 3

[0091] This example provides a Z-N catalyst prepared by the following steps:

[0092] Z-N catalyst preparation: In a 250 ml glass reactor, 2 g of the above-mentioned carrier POP-2 prepared using 4-allyl catechol dibenzoate functional monomer was added, 100 ml of toluene was added, stirred, and then 10 ml of 3M benzyl magnesium chloride reagent was added at 35°C, stirred for 2 hours, filtered, washed twice with toluene, 50 ml of toluene was added, and then the temperature was increased to 50°C, 40 ml of TiCl4was slowly added dropwise, reacted for 2 hours, and then the temperature was increased to 80°C, reacted for 3 hours, after the reaction was completed, filtered, 50 ml of toluene and 30 ml of TiCl4were added, reacted at 80°C for 2 hours, filtered after the reaction was completed, washed with toluene and hexane each 3 times, and after drying, free-flowing catalyst particles were obtained, which was recorded as Cat-3, the Mg content of the catalyst Cat-3 was 3.2%, the titanium content was 3.0%, and the organic polymer carrier content was 78%.

[0093] Example 4

[0094] The present embodiment provides a Z-N catalyst prepared by the following steps:

[0095] (1) Preparation of a porous organic polymer carrier:

[0096] In a 250 ml glass reactor, 100 ml of ethanol, 20 ml of water, and 15 ml of ethyl acetate were added, then 6.0 g of divinylbenzene (Aldrin reagent, 80%) and 3.0 g of 4-allyl-6-bromo catechol diisobutyrate were added, stirred at room temperature for 5 min, then 2% of the mass of the monomer of a block copolymer of polyethylene oxide and polypropylene oxide F127 was added, stirred at 45°C for 1 h to completely dissolve the stabilizer, 2.0% of the mass of the monomer of benzoyl peroxide BPO was added, the temperature was increased to 70°C, reacted for 3 hours, and then the temperature was increased to 80°C, reacted for 8 hours, the stirring speed was 550 rpm, after filtration, 100 ml of a mixed solvent of ethanol and water (9:1 by volume) was added and washed 3 times, filtered, and dried to obtain 7.1 g of a free-flowing porous organic polymer carrier POP-3. The specific surface area of the carrier was 328 m 2 / g, the pore volume was 0.45 ml / g;

[0097] (2) Z-N catalyst preparation:

[0098] In a 250 ml glass reactor, 3 g of the above prepared porous organic polymer POP-3 was added, 100 ml of toluene was added, stirred, then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at 35 °C, stirred for 2 hours, after filtration, washed twice with toluene, then 50 ml of toluene was added, then heated to 50 °C, 30 ml of TiCl4was added dropwise, reacted for 2 hours, then heated to 80 °C, after the reaction was completed, filtered, washed with toluene and hexane each for 3 times, dried to obtain free-flowing catalyst particles, recorded as Cat-4, the Mg content of the catalyst Cat-4 was 2.5%, the Ti content was 2.2%, and the organic polymer carrier content was 83%.

[0099] Example 5

[0100] This example provides a Z-N catalyst prepared by the following steps:

[0101] Preparation of Z-N catalyst: In a 250 ml glass reactor, 3 g of the above prepared porous organic polymer POP-3 was added, 100 ml of toluene was added, stirred, then 10 ml of 3M methyl magnesium chloride Grignard reagent was added at room temperature, stirred for 3 hours, after filtration, washed twice with toluene, then 50 ml of toluene was added, then heated to 50 °C, 30 ml of TiCl4was added dropwise, reacted for 2 hours, then heated to 80 °C, 0.25 g of diisobutyl phthalate internal electron donor was added, reacted for 3 hours, after the reaction was completed, filtered, washed with toluene and hexane each for 3 times, dried to obtain free-flowing catalyst particles, recorded as Cat-5, the Mg content of the catalyst Cat-5 was 3.0%, the Ti content was 2.1%, the internal electron donor content was 3.1%, and the organic polymer carrier content was 76%.

[0102] Example 6

[0103] This example provides a Z-N catalyst prepared by the following steps:

[0104] (1) Preparation of porous organic polymer carrier:

[0105] In a 250ml glass reactor, 90ml of ethanol, 10ml of water and 30ml of butyl acetate were added, then 6.0g of divinylbenzene (Aldrich reagent, 55%) and 4.0g of 4-allyl-6-bromoresorcinol diacetate were added, stirred for 5min at room temperature, then 5% of monomer mass of polyethylene oxide and polypropylene oxide block copolymer F127 was added, stirred at 45°C for 1h to completely dissolve the stabilizer, 2.0% of monomer mass of AIBN was added, heated to 70°C, reacted for 3h, then the temperature was raised to 80°C, reacted for 8h, the stirring speed was 600rpm, after filtration, 100ml of mixed solvent of ethanol and water (9:1 by volume) was added for washing 3 times, after filtration and drying, 6.3g of free-flowing porous organic polymer support POP-4 was obtained. The specific surface area of the support was 249m 2 / g, the pore volume was 0.49ml / g;

[0106] (2) Preparation of Z-N catalyst:

[0107] In a 250ml glass reactor, 3g of the above-mentioned support POP-4 prepared from 4-allyl-6-bromoresorcinol diacetate functional monomer was added, 100ml of toluene was added and stirred, then 10ml of 3M butyl magnesium bromide reagent was added at 35°C, stirred for 2h, after filtration, washed with toluene for 2 times, then 60ml of toluene was added, heated to 50°C, and 30ml of TiCl4 was added dropwise, reacted for 2h, then heated to 80°C, reacted for 3h, after the reaction was completed, filtered, washed with toluene and hexane for 3 times respectively, and dried to obtain free-flowing catalyst particles, which were recorded as Cat-6. The Mg content of the catalyst Cat-6 was 2.5%, the titanium content was 2.5%, and the organic polymer support content was 78%.

[0108] Example 7

[0109] This example provides a Z-N catalyst prepared by the following steps:

[0110] (1) Preparation of porous organic polymer support:

[0111] In a 250 ml glass reactor, 110 ml of ethanol, 12 ml of water and 20 ml of tetrahydrofuran were added, then 6.0 g of divinylbenzene (Aldrin reagent, 80%) and 3.0 g of 4-allyl-6-bromoresorcinol dibenzoate were added, stirred at room temperature for 5 min, then 2% of monomer mass of polyethylene oxide and polypropylene oxide block copolymer F127 was added, stirred at 45°C for 1 h, the stabilizer was completely dissolved, 2.0% of monomer mass of AIBN was added, the temperature was raised to 70°C, and reacted for 3 h, then the temperature was raised to 80°C, and reacted for 8 h, the stirring speed was 550 rpm, after filtration, 100 ml of a mixed solvent of ethanol and water (9:1 by volume) was added for washing 3 times, and after filtration and drying, 6.5 g of a free-flowing porous organic polymer support POP-5 was obtained. The specific surface area of the support was 527 m 2 / g, and the pore volume was 0.41 ml / g.

[0112] (2) Preparation of Z-N catalyst:

[0113] In a 250 ml glass reactor, 3 g of the above-mentioned support POP-5 prepared from 4-allyl-6-bromoresorcinol dibenzoate functional monomer was added, 100 ml of toluene was added and stirred, then 12 ml of 3M di-n-butyl magnesium was added at room temperature, stirred for 3 h, after filtration, washed with toluene for 2 times, then 50 ml of toluene was added, and the temperature was raised to 50°C, and 30 ml of TiCl4 was slowly added dropwise, reacted for 2 h, then the temperature was raised to 80°C, filtered, 100 ml of TiCl4 was added and reacted at 80°C for 2 h, after filtration, washed with toluene and hexane for 3 times, and dried to obtain free-flowing catalyst particles, which were recorded as Cat-7. The Mg content of the catalyst Cat-7 was 3.2%, the titanium content was 3.7%, and the organic polymer support content was 74%.

[0114] Example 8

[0115] This example provides a Z-N catalyst prepared by the following steps:

[0116] (1) Preparation of a porous organic polymer support:

[0117] In a 250 ml glass reactor, 100 ml of ethanol, 10 ml of water and 15 ml of tetrahydrofuran were added, then 6.0 g of divinylbenzene (Aldrin reagent, 80%) and 2.5 g of 4-allyl-6-bromoresorcinol dibenzoate and 1.0 g of hydroxyethyl methacrylate were added, stirred at room temperature for 5 min, then 2% of the mass of the monomer of a block copolymer of polyethylene oxide and polypropylene oxide F127 was added, stirred at 45°C for 1 h to completely dissolve the stabilizer, 2.0% (3.0 g) of the mass of the monomer of AIBN was added, the temperature was raised to 70°C, and reacted for 3 hours, then the temperature was raised to 80°C, and reacted for 8 hours, the stirring speed was 350 rpm, after filtration, 100 ml of a mixed solvent of ethanol and water (9:1 by volume) was added for washing 3 times, and after filtration and drying, 7.2 g of a free-flowing porous organic polymer carrier POP-6 was obtained. The specific surface area of the carrier was 352 m 2 / g, the pore volume was 0.33 ml / g;

[0118] (2) Preparation of Z-N catalyst:

[0119] In a 250 ml glass reactor, 3 g of the carrier POP-6 prepared from the 4-allyl-6-bromoresorcinol dibenzoate functional monomer and the third monomer hydroxyethyl methacrylate was added, 100 ml of toluene was added and stirred, then 15 ml of 3M methylmagnesium chloride reagent was added at 20°C, stirred for 2 hours, filtered, washed with toluene twice, then 50 ml of toluene was added, and then the temperature was raised to 50°C, and 30 ml of TiCl4 was slowly added dropwise, reacted for 2 hours, then the temperature was raised to 80°C, 0.20 g of 9,9-dimethoxyfluorene internal electron donor was added, and reacted for 3 hours, after the reaction was completed, filtration was performed, then 100 ml of TiCl4 was added and reacted at 80°C for 1 hour, after filtration, toluene and hexane were each washed 3 times, and after drying, free-flowing catalyst particles were obtained, which were recorded as Cat-8. The Mg content of the catalyst Cat-8 was 4.5%, the titanium content was 2.1%, the internal electron donor content was 1.9%, and the organic polymer carrier content was 73%.

[0120] Example 9

[0121] This example provides a Z-N catalyst prepared by the following steps:

[0122] Z-N catalyst preparation: In a 250 ml glass reactor, 3 g of the support POP-6 prepared from 4-allyl-6-bromo catechol dibenzoate functional monomer and the third monomer hydroxyethyl methacrylate was added, 100 ml of toluene was added, stirred, then 12 ml of 3M methyl magnesium chloride reagent was added at 20°C, stirred for 2 hours, after filtration, washed twice with toluene, then heated to 80°C, 50 ml of toluene was added, 50 ml of TiCl4was slowly added dropwise, reacted for 3 hours, after the reaction was completed, filtered, washed with toluene, hexane each 3 times, dried to obtain free-flowing catalyst particles, recorded as Cat-9, the Mg content of the catalyst Cat-9 was 3.7%, the titanium content was 3.0%, and the organic polymer support content was 75%.

[0123] Comparative Example 1

[0124] This comparative example provides a Z-N catalyst prepared by the following steps:

[0125] Inorganic support loaded Z-N polypropylene catalyst preparation: In a 250 ml glass reactor, 3 g of spherical ethoxymagnesium support (Japan Zeon Corporation) was added, 100 ml of toluene was added, stirred, then 50 ml of TiCl4was slowly added dropwise at 0°C, the dropping speed was controlled to control the temperature at 0-5°C, after the addition was completed, the temperature was raised to 60°C, 0.30 g of DIBP internal electron donor was added, reacted at 110°C for 2 hours, after filtration, 100 ml of fresh TiCl4was added, reacted at 110°C for 2 hours, after the reaction was completed, filtered, washed with toluene, hexane each 3 times, dried to obtain free-flowing catalyst particles, recorded as Cat-10, the titanium content of the catalyst Cat-10 was 3.2%, and the DIBP internal electron donor content was 8.9%.

[0126] Comparative Example 2

[0127] This comparative example provides a Z-N catalyst prepared by the following steps:

[0128] Preparation of inorganic support loaded Z-N polypropylene catalyst: In a 250 ml glass reactor, 3 g of spherical ethoxylated magnesium support (Showa Denko, Japan) was taken, 50 ml of toluene was added, stirred and then 30 ml of TiCl4was added slowly drop wise at 50 °C for 2 hours, then temperature was raised to 80 °C and 0.20 g of 9,9-dimethoxyfluorene internal donor was added and reacted for 3 hours, after completion of the reaction, filtered, again 100 ml of TiCl4was added and reacted at 80 °C for 1 hour, after completion of the reaction, filtered, washed with toluene, hexane each for 3 times, dried to get free flowing catalyst particles, noted as Cat-13, titanium content of the catalyst Cat-13 was 3.4% and 9,9-dimethoxyfluorene internal donor content was 3.7%.

[0129] Comparative Example 3

[0130] The present comparative example provides an inorganic support loaded Z-N catalyst which was prepared by the following steps:

[0131] In a 250 ml glass reactor, 3 g of spherical ethoxylated magnesium support (Showa Denko, Japan) was taken, 50 ml of toluene was added, stirred and then 30 ml of TiCl4was added slowly drop wise at 50 °C for 2 hours, then temperature was raised to 80 °C and 0.20 g of 9,9-dimethoxyfluorene internal donor was added and reacted for 3 hours, after completion of the reaction, filtered, again 100 ml of TiCl4was added and reacted at 80 °C for 1 hour, after completion of the reaction, filtered, washed with toluene, hexane each for 3 times, dried to get free flowing catalyst particles, noted as Cat-13, titanium content of the catalyst Cat-13 was 3.4% and 9,9-dimethoxyfluorene internal donor content was 3.7%.

[0132] Comparative Example 4

[0133] The present comparative example provides an inorganic support loaded Z-N catalyst which was prepared by the following steps:

[0134] In a 250 ml glass reactor, 3 g of spherical ethoxylated magnesium support (Showa Denko, Japan) was taken, 50 ml of toluene was added, stirred and then 30 ml of TiCl4was added slowly drop wise at 50 °C for 2 hours, then temperature was raised to 80 °C and 0.20 g of 9,9-dimethoxyfluorene internal donor was added and reacted for 3 hours, after completion of the reaction, filtered, again 100 ml of TiCl4was added and reacted at 80 °C for 1 hour, after completion of the reaction, filtered, washed with toluene, hexane each for 3 times, dried to get free flowing catalyst particles, noted as Cat-13, titanium content of the catalyst Cat-13 was 3.4% and 9,9-dimethoxyfluorene internal donor content was 3.7%.

[0135] Propylene polymerization

[0136] Test Example 1

[0137] Into a 10 L dry polymerization reactor for propylene, 2.0 kg of liquid propylene, 10 ml of triethylaluminium TEA (1.0 mole / litre), and 600 rpm of stirring speed were introduced. Then, 80 mg of catalyst Cat-2 and 0.3 ml of cyclohexylmethyldimethoxysilane (C-donor) were added, and 0.5 g of hydrogen was added. The temperature was raised to 70°C, and the polymerization was carried out for 1 hour under stirring at 600 rpm. After the completion of the reaction, the reaction was terminated, and the product was cooled to room temperature. After drying, 840 g of polypropylene product (PP-3) was obtained, with a bulk density of 0.38 g / ml, and a catalyst activity of 10500 gPP / gcat.h, as shown in Table 1.

[0138] Test Example 2

[0139] Into a 10 L dry polymerization reactor for propylene, 2.0 kg of liquid propylene, 10 ml of triethylaluminium TEA (1.0 mole / litre), and 600 rpm of stirring speed were introduced. Then, 80 mg of catalyst Cat-2 and 0.3 ml of cyclohexylmethyldimethoxysilane (C-donor) were added, and 0.5 g of hydrogen was added. The temperature was raised to 70°C, and the polymerization was carried out for 1 hour under stirring at 600 rpm. After the completion of the reaction, the reaction was terminated, and the product was cooled to room temperature. After drying, 840 g of polypropylene product (PP-3) was obtained, with a bulk density of 0.38 g / ml, and a catalyst activity of 10500 gPP / gcat.h, as shown in Table 1.

[0140] Test Example 3

[0141] Into a 10 L dry polymerization reactor for propylene, 2.0 kg of liquid propylene, 10 ml of triethylaluminium TEA (1.0 mole / litre), and 600 rpm of stirring speed were introduced. Then, 80 mg of catalyst Cat-2 and 0.3 ml of cyclohexylmethyldimethoxysilane (C-donor) were added, and 0.5 g of hydrogen was added. The temperature was raised to 70°C, and the polymerization was carried out for 1 hour under stirring at 600 rpm. After the completion of the reaction, the reaction was terminated, and the product was cooled to room temperature. After drying, 840 g of polypropylene product (PP-3) was obtained, with a bulk density of 0.38 g / ml, and a catalyst activity of 10500 gPP / gcat.h, as shown in Table 1.

[0142] Test Example 4

[0143] Into a 10 L dry polymerization reactor for propylene, 2.0 kg of liquid propylene, 10 ml of triethylaluminium TEA (1.0 mole / litre), and a stirring speed of 600 rpm were introduced. Then, 80 mg of catalyst Cat-3 and 0.3 ml of cyclohexylmethyldimethoxysilane (C-external donor) were added. 0.5 g of hydrogen was added, the temperature was raised to 70 °C, and the polymerization was carried out for 1 hour at a stirring speed of 600 rpm. After the completion of the reaction, the reaction was terminated, the temperature was cooled to room temperature, and the product was dried to obtain 1048 g of polypropylene (PP-4) having a bulk density of 0.40 g / ml and a catalyst activity of 13100 gPP / gcat.h, as shown in Table 1.

[0144] Test Example 5

[0145] Into a 10 L dry polymerization reactor for propylene, 2.0 kg of liquid propylene, 10 ml of triethylaluminium TEA (1.0 mole / litre), and a stirring speed of 600 rpm were introduced. Then, 80 mg of catalyst Cat-3 and 0.3 ml of cyclohexylmethyldimethoxysilane (C-external donor) were added. 0.5 g of hydrogen was added, the temperature was raised to 70 °C, and the polymerization was carried out for 1 hour at a stirring speed of 600 rpm. After the completion of the reaction, the reaction was terminated, the temperature was cooled to room temperature, and the product was dried to obtain 1048 g of polypropylene (PP-4) having a bulk density of 0.40 g / ml and a catalyst activity of 13100 gPP / gcat.h, as shown in Table 1.

[0146] Test Example 6

[0147] Into a 10 L dry polymerization reactor for propylene, 2.0 kg of liquid propylene, 10 ml of triethylaluminium TEA (1.0 mole / litre), and a stirring speed of 600 rpm were introduced. Then, 80 mg of catalyst Cat-3 and 0.3 ml of cyclohexylmethyldimethoxysilane (C-external donor) were added. 0.5 g of hydrogen was added, the temperature was raised to 70 °C, and the polymerization was carried out for 1 hour at a stirring speed of 600 rpm. After the completion of the reaction, the reaction was terminated, the temperature was cooled to room temperature, and the product was dried to obtain 1048 g of polypropylene (PP-4) having a bulk density of 0.40 g / ml and a catalyst activity of 13100 gPP / gcat.h, as shown in Table 1.

[0148] Test Example 7

[0149] Into a 10 L dry polymerization reactor for propylene, 2.0 kg of liquid propylene, 10 ml of triethylaluminium TEA (1.0 mole / litre), and a stirring speed of 600 rpm were introduced. Then, 80 mg of catalyst Cat-6 and 0.5 ml of dicyclopentadiene dimethoxysilane (D-external donor) were added, 0.7 g of hydrogen was added, the temperature was raised to 70 °C, and the polymerization was carried out at a stirring speed of 600 rpm for 1 hour. After the completion of the reaction, the reaction was terminated, the temperature was lowered to room temperature, and after drying, 900 g of polypropylene product (PP-7) was obtained, having a bulk density of 0.38 g / ml and a catalyst activity of 11250 gPP / gcat.h, as shown in Table 1.

[0150] Test Example 8

[0151] Into a 10 L dry polymerization reactor for propylene, 2.0 kg of liquid propylene, 10 ml of triethylaluminium TEA (1.0 mole / litre), and a stirring speed of 600 rpm were introduced. Then, 80 mg of catalyst Cat-6 and 0.5 ml of dicyclopentadiene dimethoxysilane (D-external donor) were added, 0.7 g of hydrogen was added, the temperature was raised to 70 °C, and the polymerization was carried out at a stirring speed of 600 rpm for 1 hour. After the completion of the reaction, the reaction was terminated, the temperature was lowered to room temperature, and after drying, 900 g of polypropylene product (PP-7) was obtained, having a bulk density of 0.38 g / ml and a catalyst activity of 11250 gPP / gcat.h, as shown in Table 1.

[0152] Test Example 9

[0153] Into a 10 L dry polymerization reactor for propylene, 2.0 kg of liquid propylene, 10 ml of triethylaluminium TEA (1.0 mole / litre), and a stirring speed of 600 rpm were introduced. Then, 80 mg of catalyst Cat-6 and 0.5 ml of dicyclopentadiene dimethoxysilane (D-external donor) were added, 0.7 g of hydrogen was added, the temperature was raised to 70 °C, and the polymerization was carried out at a stirring speed of 600 rpm for 1 hour. After the completion of the reaction, the reaction was terminated, the temperature was lowered to room temperature, and after drying, 900 g of polypropylene product (PP-7) was obtained, having a bulk density of 0.38 g / ml and a catalyst activity of 11250 gPP / gcat.h, as shown in Table 1.

[0154] Test Example 10

[0155] Into a 10 L dry polymerization reactor for propylene, 2.0 kg of liquid propylene, 10 ml of triethylaluminium TEA (1.0 mole / litre), and a stirring speed of 600 rpm were introduced. Then, 80 mg of catalyst Cat-9 and 0.3 ml of cyclohexylmethyldimethoxysilane (C-donor) were added, 0.5 g of hydrogen was added, the temperature was raised to 70 °C, and the polymerization was carried out for 1 hour at a stirring speed of 600 rpm. After the completion of the reaction, the reaction was terminated, the temperature was lowered to room temperature, and after drying, 1000 g of polypropylene product (PP-10) was obtained, having a bulk density of 0.40 g / ml and a catalyst activity of 12500 gPP / gcat.h, as shown in Table 1.

[0156] Comparative Test Example 1

[0157] Into a 10 L dry polymerization reactor for propylene, 2.0 kg of liquid propylene, 10 ml of triethylaluminium TEA (1.0 mole / litre), and a stirring speed of 600 rpm were introduced. Then, 80 mg of catalyst Cat-9 and 0.3 ml of cyclohexylmethyldimethoxysilane (C-donor) were added, 0.5 g of hydrogen was added, the temperature was raised to 70 °C, and the polymerization was carried out for 1 hour at a stirring speed of 600 rpm. After the completion of the reaction, the reaction was terminated, the temperature was lowered to room temperature, and after drying, 1000 g of polypropylene product (PP-10) was obtained, having a bulk density of 0.40 g / ml and a catalyst activity of 12500 gPP / gcat.h, as shown in Table 1.

[0158] Comparative Test Example 2

[0159] Into a 10 L dry polymerization reactor for propylene, 2.0 kg of liquid propylene, 10 ml of triethylaluminium TEA (1.0 mole / litre), and a stirring speed of 600 rpm were introduced. Then, 80 mg of catalyst Cat-9 and 0.3 ml of cyclohexylmethyldimethoxysilane (C-donor) were added, 0.5 g of hydrogen was added, the temperature was raised to 70 °C, and the polymerization was carried out for 1 hour at a stirring speed of 600 rpm. After the completion of the reaction, the reaction was terminated, the temperature was lowered to room temperature, and after drying, 1000 g of polypropylene product (PP-10) was obtained, having a bulk density of 0.40 g / ml and a catalyst activity of 12500 gPP / gcat.h, as shown in Table 1.

[0160] Comparative Test Example 3

[0161] A 10 L dry polymerization reactor was charged with 2.0 kg of liquid propylene, 10 mL of triethylaluminum TEA (1.0 mole / L), and stirred at 600 rpm. Then, 60 mg of comparative catalyst Cat-12 was added, followed by 0.3 mL of cyclohexylmethyldimethoxysilane (external donor), 0.5 g of hydrogen gas, and the temperature was raised to 70 °C. The polymerization was carried out at 600 rpm for 1 h. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 948 g of polypropylene product (PP-13) with a bulk density of 0.38 g / mL and a catalyst activity of 15,800 gPP / gcat.h, as shown in Table 1.

[0162] Comparative Test Example 4

[0163] A 10 L dry polymerization reactor was charged with 2.0 kg of liquid propylene, 10 mL of triethylaluminum TEA (1.0 mole / L), and stirred at 600 rpm. Then, 60 mg of comparative catalyst Cat-12 was added, followed by 0.3 mL of cyclohexylmethyldimethoxysilane (external donor), 0.5 g of hydrogen gas, and the temperature was raised to 70 °C. The polymerization was carried out at 600 rpm for 1 h. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 948 g of polypropylene product (PP-13) with a bulk density of 0.38 g / mL and a catalyst activity of 15,800 gPP / gcat.h, as shown in Table 1.

[0164] Table 1. Propylene polymerization results

[0165]

[0166] Test Example 11. Copolymerization of propylene and ethylene

[0167] A 10 L dry polymerization reactor was charged with 2.0 kg of liquid propylene, 10 mL of triethylaluminum TEA (1.0 mole / L), and stirred at 600 rpm. Then, 60 mg of comparative catalyst Cat-12 was added, followed by 0.3 mL of cyclohexylmethyldimethoxysilane (external donor), 0.5 g of hydrogen gas, and the temperature was raised to 70 °C. The polymerization was carried out at 600 rpm for 1 h. After the reaction was completed, the reaction was terminated, cooled to room temperature, and dried to obtain 948 g of polypropylene product (PP-13) with a bulk density of 0.38 g / mL and a catalyst activity of 15,800 gPP / gcat.h, as shown in Table 1.

[0168] Test Example 12. Copolymerization of propylene and ethylene

[0169] Into a 10 L dry polymerization reactor for propylene, 2.0 kg liquid propylene, 10 ml triethylaluminium TEA (1.0 mole / litre), stirring speed 600 rpm, then add Cat-3 catalyst 60 mg, and 0.5 ml cyclohexylmethyldimethoxysilane (external donor), add 0.5 g hydrogen gas and 50 g ethylene monomer, temperature raised to 70 °C, polymerize for 1 hour at 600 rpm, after completion of reaction, terminate the reaction, cool to room temperature, dry to get 936 g of ethylene propylene copolymer product, catalyst activity 15,600 g PP / g cat.h, polymer weight average molecular weight Mw 63.2 million g / mol, molecular weight distribution coefficient 9.1.

[0170] Test example 13 propylene with ethylene copolymerization

[0171] Into a 10 L dry polymerization reactor for propylene, 2.0 kg liquid propylene, 10 ml triethylaluminium TEA (1.0 mole / litre), stirring speed 600 rpm, then add Cat-3 catalyst 60 mg, and 0.5 ml cyclohexylmethyldimethoxysilane (external donor), add 0.5 g hydrogen gas and 50 g ethylene monomer, temperature raised to 70 °C, polymerize for 1 hour at 600 rpm, after completion of reaction, terminate the reaction, cool to room temperature, dry to get 936 g of ethylene propylene copolymer product, catalyst activity 15,600 g PP / g cat.h, polymer weight average molecular weight Mw 63.2 million g / mol, molecular weight distribution coefficient 9.1.

[0172] Test example 14 propylene with butene copolymerization

[0173] Into a 10 L dry polymerization reactor for propylene, 2.0 kg liquid propylene, 10 ml triethylaluminium TEA (1.0 mole / litre), stirring speed 600 rpm, then add Cat-3 catalyst 60 mg, and 0.5 ml cyclohexylmethyldimethoxysilane (external donor), add 0.5 g hydrogen gas and 50 g ethylene monomer, temperature raised to 70 °C, polymerize for 1 hour at 600 rpm, after completion of reaction, terminate the reaction, cool to room temperature, dry to get 936 g of ethylene propylene copolymer product, catalyst activity 15,600 g PP / g cat.h, polymer weight average molecular weight Mw 63.2 million g / mol, molecular weight distribution coefficient 9.1.

[0174] From the above polymerization results, it can be seen that the organic carrier loaded POP-Ph-(OCO)2 / RMgX / TiCl4 polypropylene catalyst solid component (internal electron donor can be selectively added) prepared by using the free radical polymerizable unsaturated double bond containing catechol ester functional monomer in the application has good catalytic activity, and the propylene homopolymerization activity can reach more than 13000 gPP / gcat.h, which is lower than that of the traditional inorganic MgCl2 carrier loaded catalyst, but the activity is greatly improved compared with the existing organic polymer carrier type polymerization activity, and can meet the level of the existing industrial catalyst. By screening the free radical polymerizable unsaturated double bond containing catechol ester functional monomer, relying on the functional groups of catechol ester on the carrier, the micro-chemical environment of the metal active center is controlled, and the organic carrier loaded POP-Ph-(OCO)2 / RMgX / TiCl4 polypropylene catalyst solid component is designed and prepared, so that the catalyst has good stereospecificity, and even without additional internal electron donor, the prepared polypropylene has high isotacticity, and the isotacticity can reach more than 98%, and the TREF high temperature elution temperature can reach 124℃, which is higher than the elution temperature (121-123℃) of the conventional isotactic polypropylene (iPP), and in addition, the polymer molecular weight distribution can be adjusted in a wide range, and the molecular weight distribution coefficient can be controlled between 8-20.

[0175] Compared with Comparative Example 1 (adding the same conventional internal electron donor such as DIBP), the isotacticity of the polymer prepared by using the catalyst Cat-5 prepared in Example 5 of the application is obviously higher than that of the catalysts in Comparative Example 1 and Comparative Example 3; compared with Comparative Example 2 and Comparative Example 4 (using the internal electron donor 9,9-dimethoxy fluorene internal electron donor with high stereoregularity and relatively narrow molecular weight distribution), the polypropylene prepared by using the catalyst Cat-8 prepared in Example 8 has higher stereoregularity, the TREF high temperature elution temperature is about 124.0℃, has a wider molecular weight distribution, and the molecular weight distribution of the polymer prepared by using the catalyst Cat-8 is 10.6.

[0176] The POP-Ph-(OCO)2 / RMgX / TiCl4 polypropylene catalyst disclosed in the application has the advantages of simple preparation method, high stereospecificity of the active center, wide molecular weight distribution, good industrialization prospect, and the like, and has advantages in developing low precipitation polypropylene and high rigid-tough balance polypropylene products.

Claims

1. A ZN catalyst, wherein the raw material composition, calculated as 100% by mass of the ZN catalyst, comprises 60-85 wt% organic polymer support, 1-5 wt% magnesium compound calculated as magnesium element, 1-5 wt% titanium compound calculated as titanium element, and 0-5 wt% internal electron donor; The organic polymer carrier is obtained by copolymerization of monomers including divinylbenzene and unsaturated catechol ester monomers; in, The unsaturated catechol ester monomer has the structure shown in Formula I: Formula I, In Formula I, R1, R2, R3, and R6 are each independently selected from hydrogen, chlorine, fluorine, bromine, C1-C6 straight-chain alkyl, C1-C6 branched alkyl, cycloalkyl, and aromatic groups; x is 0-3; R4 and R5 are each independently selected from C1-C8 straight-chain hydrocarbon, C1-C8 branched hydrocarbon, cycloalkyl, and aromatic groups; Based on the organic polymer carrier mass being 100%, the mass fraction of the unsaturated catechol ester monomer is 20-70%. The specific surface area of ​​the organic polymer carrier is 100-600 m². 2 / g, pore volume > 0.2 ml / g.

2. The ZN catalyst according to claim 1, wherein, In Formula I, R1, R2, R3, and R6 are each independently selected from hydrogen, methyl, isobutyl, chlorine, fluorine, and bromine; R4 and R5 are each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl, n-heptyl, 2-methylhexyl, 2-ethylpentyl, and phenyl. x is 0 or 1.

3. The ZN catalyst according to claim 1, wherein, The unsaturated catechol ester monomers are selected from 4-allyl catechol diacetate, 4-allyl catechol dipropionate, 4-allyl catechol di-n-butyrate, 4-allyl catechol diisobutyrate, 4-allyl catechol di-n-valerate, 4-allyl catechol di-n-hexanoate, 4-allyl catechol di-n-octanoate, 4-allyl catechol diisooctanoate, 4-allyl catechol di(2-methylheptanoate), 4-allyl catechol di(2-ethylhexanoate), 4-allyl catechol dibenzoate, 4-vinyl catechol diacetate, 4-vinyl catechol dipropionate, 4-vinyl catechol di-n-butyrate, and 4-vinyl catechol diisobutyrate. Esters, 4-vinylcatechol di-n-valerate, 4-vinylcatechol di-n-hexanoate, 4-vinylcatechol di-n-octanoate, 4-vinylcatechol diisooctanoate, 4-vinylcatechol di(2-methylheptanoate), 4-vinylcatechol di(2-ethylhexanoate), 4-vinylcatechol dibenzoate, 4-allyl-6-methylcatechol diacetate, 4-allyl-6-methylcatechol dipropionate, 4-allyl-6-methylcatechol di-n-butyrate, 4-allyl-6-methylcatechol diisobutyrate, 4-allyl-6-methylcatechol di-n-valerate, 4-allyl-6-methylcatechol di-n-hexanoate, 4-allyl-6-methylcatechol di-n-hexanoate 4-Allyl-6-methylcatechol di-n-octanoate, 4-Allyl-6-methylcatechol di-(2-methylheptanoic acid) ester, 4-Allyl-6-methylcatechol di-(2-ethylhexanoic acid) ester, 4-Allyl-6-methylcatechol dibenzoate, 4-Allyl-6-isobutylcatechol diacetate, 4-Allyl-6-isobutylcatechol dipropionate, 4-Allyl-6-isobutylcatechol di-n-butyrate, 4-Allyl-6-isobutylcatechol di-isobutyrate, 4-Allyl-6-isobutylcatechol di-n-valerate, 4-Allyl-6-isobutylcatechol di-n-hexanoate, 4-Allyl-6-isobutylcatechol di-n-octanoate 4-Allyl-6-isobutylcatechol diisooctanoate, 4-Allyl-6-isobutylcatechol di(2-methylheptanoic acid) ester, 4-Allyl-6-isobutylcatechol di(2-ethylhexanoic acid) ester, 4-Allyl-6-isobutylcatechol dibenzoate, 4-Allyl-6-chlorocatechol diacetate, 4-Allyl-6-chlorocatechol dipropionate, 4-Allyl-6-chlorocatechol di-n-butyrate, 4-Allyl-6-chlorocatechol diisobutyrate, 4-Allyl-6-chlorocatechol di-n-valerate, 4-Allyl-6-chlorocatechol di-n-hexanoate, 4-Allyl-6-chlorocatechol di-n-octanoate, 4-Allyl-6-chlorocatechol diisooctanoate,4-Allyl-6-chlorocatechol di(2-methylheptanoic acid), 4-Allyl-6-chlorocatechol di(2-ethylhexanoic acid), 4-Allyl-6-chlorocatechol dibenzoate, 4-Allyl-6-fluorocatechol diacetate, 4-Allyl-6-fluorocatechol dipropionate, 4-Allyl-6-fluorocatechol di-n-butyrate, 4-Allyl-6-fluorocatechol diisobutyrate, 4-Allyl-6-fluorocatechol di-n-valerate, 4-Allyl-6-fluorocatechol di-n-hexanoate, 4-Allyl- 6-Fluoro-Catechol di-n-octanoate, 4-Allyl-6-fluoro-catechol diisooctanoate, 4-Allyl-6-fluoro-catechol di(2-methylheptanoic acid) ester, 4-Allyl-6-fluoro-catechol di(2-ethylhexanoic acid) ester, 4-Allyl-6-fluoro-catechol dibenzoate, 4-Allyl-6-bromo-catechol diacetate, 4-Allyl-6-bromo-catechol dipropionate, 4-Allyl-6-bromo-catechol di-n-butyrate, 4-Allyl-6-bromo-catechol diisobutyrate, 4-Allyl-6-bromo-catechol diisobutyrate, 4-Allyl-6-bromo-catechol diisobutyrate, 4-Allyl-6-bromo-catechol di-n-butyrate Phenyl dipentanoate, 4-allyl-6-bromocatechol dihexanoate, 4-allyl-6-bromocatechol dioctanoate, 4-allyl-6-bromocatechol diisooctanoate, 4-allyl-6-bromocatechol di(2-methylheptanoic acid), 4-allyl-6-bromocatechol di(2-ethylhexanoic acid), 4-allyl-6-bromocatechol dibenzoate, 4-(1-chloroallyl)catechol diacetate, 4-(1-chloroallyl)catechol dipropionate, 4-(1-chloroallyl)catechol di-n- Butyrate, 4-(1-chloroallyl)catechol diisobutyrate, 4-(1-chloroallyl)catechol di-n-valerate, 4-(1-chloroallyl)catechol di-n-hexanoate, 4-(1-chloroallyl)catechol di-n-octanoate, 4-(1-chloroallyl)catechol diisooctanoate, 4-(1-chloroallyl)catechol di(2-methylheptanoic acid), 4-(1-chloroallyl)catechol di(2-ethylhexanoic acid), and 4-(1-chloroallyl)catechol dibenzoate are all selected from the group consisting of one or more of these.

4. The ZN catalyst according to claim 1, wherein, The method for preparing the organic polymer carrier includes the following steps: The organic polymer carrier is prepared by copolymerization using monomers including the divinylbenzene, the unsaturated catechol ester monomers and additional monomers as raw materials; The mass ratio of the additional monomer to divinylbenzene is 0-1:1; the mass ratio of the unsaturated catechol ester monomer to divinylbenzene is 0.2-2:

1.

5. The ZN catalyst according to claim 4, wherein, The organic polymer carrier is prepared by dispersion polymerization, precipitation polymerization, suspension polymerization or emulsion polymerization. The dispersion polymerization method includes the following steps: adding divinylbenzene, unsaturated catechol ester monomers and additional monomers to a dispersion solvent, then adding a stabilizer and an initiator, stirring and dispersing, and reacting at 50-80℃ for 5-12 hours to obtain the organic polymer carrier.

6. The ZN catalyst according to claim 4, wherein, The additional monomers include one or more of styrene, alkyl-substituted styrene, chloromethyl-substituted styrene, methacrylic acid, methacrylate, and hydroxyalkyl methacrylate.

7. The ZN catalyst according to claim 5, wherein, The dispersion solvent includes C1-C4 alcohols, water, and additional solvents, wherein the additional solvents include tetrahydrofuran and / or fatty acid esters; The mass ratio of the C1-C4 alcohol to water is 5-15:1; the mass ratio of the additional solvent to the C1-C4 alcohol is 0-2:

1.

8. The ZN catalyst according to claim 7, wherein, The C1-C4 alcohols include one or more of methanol, ethanol, propanol, isopropanol, 1-butanol, and isobutanol.

9. The ZN catalyst according to claim 7, wherein, The fatty acid esters include ethyl acetate and / or butyl acetate.

10. The ZN catalyst according to claim 5, wherein, The mass ratio of the total amount of monomer added to the dispersing solvent is 1:5-20.

11. The ZN catalyst according to claim 5, wherein, The stabilizer is polyvinyl alcohol and / or polypropylene oxide-ethylene oxide copolymer.

12. The ZN catalyst according to claim 5, wherein, The weight-average molecular weight of the stabilizer is 1,000-100,000.

13. The ZN catalyst according to claim 5, wherein, The mass ratio of the amount of stabilizer added to the total amount of monomer added is 0.5-5:

100.

14. The ZN catalyst according to claim 5, wherein, The initiator is azobisisobutyronitrile and / or benzoyl peroxide.

15. The ZN catalyst according to claim 5, wherein, The mass ratio of the amount of initiator added to the total amount of monomer added is 0.5-3:

100.

16. The ZN catalyst according to claim 4, wherein, The divinylbenzene is a pretreated divinylbenzene, wherein the pretreatment is to remove the polymerization inhibitor.

17. The ZN catalyst according to claim 1, wherein, The organic polymer carrier contains 65-80 wt%, magnesium 2-4 wt%, and titanium 2-4 wt%.

18. The ZN catalyst according to claim 1, wherein, The magnesium compound is RMgX or R'MgR''; R, R', and R'' are each independently selected from C1-C8 alkyl, aryl, and alkoxy groups, and X is fluorine, chlorine, bromine, or iodine.

19. The ZN catalyst according to claim 18, wherein, R, R', and R'' are each independently selected from methyl, ethyl, propyl, butyl, alkoxy, phenyl, and substituted phenyl.

20. The ZN catalyst according to claim 18, wherein, The magnesium compound is one or a combination of two or more of alkyl halide magnesium compounds, alkyl magnesium compounds, and alkoxy halide magnesium compounds.

21. The ZN catalyst according to claim 20, wherein, The magnesium compound includes one or more of the following: methyl magnesium chloride, n-butyl magnesium chloride, isobutyl magnesium chloride, tert-butyl magnesium chloride, benzyl magnesium chloride, ethyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, n-butyl magnesium bromide, benzyl magnesium bromide, methyl magnesium iodide, tert-butyl magnesium iodide, benzyl magnesium iodide, n-butyl magnesium iodide, methyl magnesium fluoride, tert-butyl magnesium fluoride, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, and ethoxy magnesium chloride.

22. The ZN catalyst according to claim 1, wherein, The titanium compound is titanium tetrachloride.

23. The ZN catalyst according to claim 1, wherein, The internal electron donor is one or a combination of two or more of the following: diester compounds, diphenol ester compounds, diol ester compounds, succinate compounds, and diether compounds.

24. The ZN catalyst according to claim 23, wherein, The internal electron donor includes one or more of the following: diisobutyl phthalate, di-n-butyl phthalate, 9,9-dimethoxyfluorene, diisobutyl 2,3-diisopropylsuccinate, 3-methyl-5-tert-butyl-1,2-benzenediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol diphenyl methyl ester, and 2-isopropyl-2-isopentyl-1,3-propanedimethyl ether.

25. A method for preparing the ZN catalyst according to any one of claims 1-24, comprising the following steps: Under anhydrous and oxygen-free conditions, the organic polymer support is added to an inert solvent, followed by the magnesium compound. After reacting at 0℃-50℃ for 15-120 minutes, the unreacted magnesium compound is filtered out. Then, an inert solvent and titanium tetrachloride are added, and the reaction is carried out at 0℃-120℃ for 15-180 minutes. Finally, the internal electron donor is added, and the reaction is carried out at 50℃-120℃ for 15-180 minutes. The mixture is then washed with an inert solvent to obtain the ZN catalyst.

26. A ZN catalyst system comprising a ZN catalyst, an external electron donor, and a co-catalyst; in, The ZN catalyst is the ZN catalyst according to any one of claims 1-24.

27. The ZN catalyst system according to claim 26, wherein, The external electron donor includes silane-based external electron donors.

28. The ZN catalyst system according to claim 27, wherein, The silane-based external electron donors include one or more combinations of cyclohexylmethyldimethoxysilane, dicyclopentenedimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, and tetraethoxysilane.

29. The ZN catalyst system according to claim 27, wherein, The molar ratio of silicon in the silane-based external electron donor to titanium in the ZN catalyst is 1-50.

30. The ZN catalyst system according to claim 26, wherein, The cocatalyst includes an alkylaluminum compound, wherein the alkylaluminum compound is Al(R''')3, and R''' is a C1-C6 alkyl group.

31. The ZN catalyst system according to claim 30, wherein, The R''' is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl.

32. The ZN catalyst system according to claim 30, wherein, The co-catalyst is triethylaluminum.

33. The ZN catalyst system according to claim 30, wherein, The molar ratio of aluminum in the alkylaluminum compound to titanium in the ZN catalyst is 10-500.

34. The application of the ZN catalyst according to any one of claims 1-24 or the ZN catalyst system according to claims 26-33 in olefin polymerization.

35. The application according to claim 34, wherein, The olefin polymerization is propylene homopolymerization, propylene-ethylene copolymerization, or α-olefin copolymerization.

36. The application according to claim 35, wherein, The α-olefin is butene and / or isobutene.

37. The application according to claim 34, wherein, The olefin polymerization is gas-phase polymerization, bulk polymerization, or slurry polymerization.

38. The application according to claim 37, wherein, The reaction temperature for slurry polymerization is 30-80℃, and the reaction pressure is 0.1-2.0 MPa.

39. The application according to claim 37, wherein, The solvent for the slurry polymerization is C5-C. 10 Alkanes.

40. The application according to claim 37, wherein, The solvent used for slurry polymerization is hexane.

41. The application according to claim 37, wherein, The reaction pressure for the bulk polymerization is 2.8-4.0 MPa, and the reaction temperature is 68-72℃.

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